Method for controlling noxious vapors

ABSTRACT

METHOD FOR SUBSTANTIALLY REMOVING NOXIOUS VAPORS LIBERATED FROM MATERIALS TREATED WITH HIGHLY HALOGENATED FLAME RETARDING AGENTS UPON EXPOSURE TO HEAT IS PROVIDED COMPRISING APPLYING TO SAID MATERIALS AN ORGANOPHOSPHORUS COMPOUND HAVING THE STRUCTURAL FORMULA:   (R&#39;&#39;)M-P(=O)(-O-R)N   WHEREIN R IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF ALKYNYL, ALKENYL AND ARALKENYL RADICALS, R&#39;&#39; IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF ALKYL, HALOALKYL AND ALKENYL RADICALS, M IS A WHOLE NUMBER FROM 0 TO 1 INCLUSIVE, AND N IS A WHOLE NUMBER FROM 2 TO 3 INCLUSIVE, SUCH THAT M+N EQUALS 3.

United States Patent 3,692,567 METHOD FOR CONTROLLING NOXIOUS VAPORS Calvin Vogel, Easton, Pa., assignor to GAF Corporation, New York, N.Y. No Drawing. Filed June I, 1971, Ser. No. 148,952 Int. Cl. B44d 1/44; C09k 3/28 U.S. Cl. 1l7--62 7 Claims ABSTRACT OF THE DISCLOSURE Method for substantially removing noxious vapors liberated from materials treated with highly halogenated flame retarding agents upon exposure to heat is provided comprising applying to said materials an organophosphorus compound having the structural formula:

0 ')mi R)= wherein R is a member selected from the group consisting of alkynyl, alkenyl and aralkenyl radicals, R is a member selected from the group consisting of alkyl, haloalkyl and alkenyl radicals, m is a whole number from 0 to l inclusive, and n is a whole number from 2 to 3 inclusive, such that m+n equals 3.

This invention relates to the use of organophosphorus compounds as getters for noxious vapors. More particularly, this invention relates to methods for substantially removing noxious vapors liberated from materials treated with highly halogenated flame retarding agents upon exposure to heat.

Natural and synthetic fibers as Well as the fabrics made therefrom are generally treated With highly halogenated flame retardants to reduce combustion hazards which may arise through use of such fabric or fibrous materials in heated areas or in areas containing exposed flames. Upon the application of heat to fibrous materials containing such highly halogenated flame retardants, noxious vapors are liberated which are lacrymal and mucous membrane irritants causing discharges from the nose and eyes and severe discomfort to those exposed to such vapors. Moreover, such vapors are sufliciently toxic to cause poisoning of those exposed thereto. The combination of such effects, for example in the midst of a fire, is sufficient to cause severe confusion and panic. Because of the extremely irritating and toxic effects of such vapors, it is often necessary for those who may be exposed thereto to wear special equipment such as gas masks and other air purifying systems. It is desirable therefor to provide a means of treating fibrous materials which contain such highly halogenated flame retardants in order to substantially eliminate the effects of the noxious vapors liberated upon heating such material.

Accordingly, it is an object of the present invention to provide getters which interact with and thereby remove the noxious vapors liberated upon heating fibrous materials treated with highly halogenated flame retardants.

It is another object of the present invention to provide getters for noxious vapors liberated upon heating fibrous materials treated with highly halogenated flame retardants which do not detract from the flame retardancy imparted to said materials by said flame retardants.

It is still another object of the present invention to improve the hand or feel of fibrous materials treated with highly halogenated flame retardants.

These as well as other objects are accomplished by the present invention which provides a method for substantially removing noxious vapors liberated from materials treated with halogenated flame retarding agents upon exposure to heat comprising applying to said material an Patented Sept. 19, 1972 organophosphorus compound having the structural formula:

-)n wherein R is a member selected from the group consisting of alkynyl, alkenyl and aralkenyl radicals, R is a member selected from the group consisting of alkyl, haloalkyl and alkenyl radicals, m is a whole number from 0 to l, inclusive, and n is a Whole number from 2 to 3, inclusive, such that m+n equals 3.

Compounds useful as getters in accordance with the present invention include the organophosphates and organophosphonates.

Typical organophosphate getters are those, for example, which can be represented by the structural formula:

wherein R is a member selected from the group consisting of alkynyl, alkenyl and aralkenyl radicals. Illustrative organophosphates are, for example, tripropargyl phosphate, trimethylbutynyl phosphate, trimethylpentynyl phosphate, tri(dimethylhexynyl) phosphate, tributynyl phosphate, triallyl phosphate, trimethallyl phosphate, tricinnamyl phosphate, tri(phenyloleyl) phosphate and the like.

Typical organophosphonates which can be employed in the present invention are those represented by the structural formula:

wherein R is a member selected from the group consisting of alkyl, haloalkyl and alkenyl and R is as defined above with respect to the organophosphates. Typical organophosphonates are, for example, dipropargyl p-chlorethyl phosphonate, dicinnamyl B-bromoethyl phosphonate, diallyl vinyl phosphonate and the like.

The getters of the present invention can be applied to fibrous materials in any suitable inert vehicle. Generally these organophosphorus compounds form solutions with tetrahydrofuran, halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, trichloroethylene and the like. It is considered preferable that the getter be present in the solution to be applied to the fibrous materials in concentrations ranging from about 5 to about 15 percent by weight. The getters can be applied to the fibrous materials in any suitable manner such as, for example, spraying, dipping, padding, immersing or blending with synthetic materials and co-extruding the resultant blend to form the fibrous materials containing the getter therein. The getters are preferably applied to the fibrous materials in suflicient quantities to insure the pick-up thereof of from about 10 to about percent by weight based on the weight of flame retardant in the fibrous material being treated. Preferably, from about 20 to about 50 percent by weight of the getter based upon the weight of flame retardance is picked up by the fibrous material.

Any natural or synthetic fiber or fabric made therefrom can be employed in accordance with the present invention. For example, fibers such as cotton, wool, silk, nylon, rayon, polyesters and the like can be beneficially treated in accordance with the present invention. Generally, these fibers or the fabrics made therefrom are made flame resistant by applying thereto highly halogenated organophosphorus compounds. Typical flame retardant compounds are for example, highly halogenated organophosphates and phosphonates. Typical of such organophosphates are, for example, the tri(2,3-dihaloallyl) phosphates such as tri(2,3-dibromoa1ly1) phosphate,

tri(2,3-dichloroallyl) phosphate and the like; di(2,3-di- Solution 2C1oth charred; vapors less noxious than from halopropyl)allyl phosphates such as di(2,3-dibromopro- 1; hand stiff; no afterglow.

pyl)allyl phosphate; diallyl (2,3-dihalopropyl) phos- Solution 3Cloth charred; vapors substantially inofphates such as diallyl (2,3-dichloropropyl) phosphate; fensive; soft hand; on afterglow. tri(2,3 dichalopropyl) phosphates such as tri(2,3-dibro- 5 Solution 4-Burned entire length, considerable char; no mopropyl) phosphate; tri(2,2,3,3-tetrahalo-propyl) phosafterglow.

phates such as tri(2,2,3,3-tetrabromopropyl) phosphate, It can be seen from the results obtained that the noxious tri(2,2,3,3 tetrachloropropyl) phosphate and the like; and vapors liberated in the absence of the getter composithe di(2,2,3,3-tetrahalopropyl) haloalkyl and alkenyl tions of the present invention are substantially eliminated phosphates such as di(2,2,3,3-tetrabromopropyl)allyl when the getter composition was present in substantially phosphate, di(2,2,3,S-tetrachloropropyl) p-chloroethyl equal amounts with the flame retardant composition.

phosphate and the like, as well as the corresponding Moreover, the hand or feel of the resultant fabric was phosphonates. These highly halogenated organophossurprisingly substantially softer. It also can be seen that phorus compounds impart flame retardation to fibers and the presence of the getter composition had no adverse fibrous materials i0 which they are applied. Generally, effect on [he flame rgtardancy imparted to the fibrous these organophosphorus compounds are applied to fibrous material by the flame retardant.

materials in any suitable inert vehicle. These compounds are usually soluble in halogenated hydrocarbons such as EXAMPLE 2 carbon tetrachloride, chloroform, trichloroethylene, per- Employing the procedure described in Example 1, a chloroethylene and the like. Solutions or dispersions consolution was prepared consisting of 5 grams of diprotaining the flame retardant compositions in concentrations pargyl 2-chloroethylphosphonate and 5 grams of ranging from about 5 to about 20% by weight are gen- OHOCH CBr CBr H) erally employed. 2 2 2 3 The flame retardant compositions can be also applied flame retardant in 45 grams of tetrahydrofuran. to fibrous materials by any convenient means such as 5 The resulting solution was sprayed onto a strip of cotspraying, dipping, immersing, padding and the like. Genton broadcloth to a 17% dry weight pick-up. When held erally, these flame retardants are applied to the fibrous in an open flame, the cloth only charred. The vapors materials in sufiicient quantities to impart to said fibrous emanating from the heated cloth were only mildly noxious materials from about 5 to about 20% by weight on a but were entirely tolerable. The hand of the treated cloth dry basis of the flame retardant composition. was soft. Once the flame was removed, no afterglow was Although not wishing to be bound by any theory or noted. mechanism, it is currently believed that 316 IIOXiOUS Although specific materials and conditions were set vapors liberated upon heating fibrous materials containf th i th above exemplary processes ki d g fiamfi retardants are Primarily attributable to the using the organophosphorus getter compositions of this high halogen concentrations thereof. It is believed that i i these, are mgrely i d d as ill i f the organic moieties contained in the getters of the present h pfesgnt i ti Various other organophosphorus invention Tfiflct with the halogens thereby y getters, vehicles, modes of application, fibers and fabrics removing saifl halogells f the vapqrs hbermed such as those listed hereinabove may be substituted in the thus substantially eliminating the potential harm and (115- examples with similar msultg comfort caused by the presence of such noxious vapors. Also it has been found that the organo phosphorus getters of the present invention do not detract from the flame retardancy imparted to the fibrous materials by the flame retardant compositions. The following examples further define, describe and compare methods of preparing and employing the organophosphorus getter compositions of the present invention. Parts and percentages are by weight unless otherwise in- Other modifications of the present invention will occur to those skilled in the art upon a reading of the present disclosure. These are intended to be included within the scope of this invention.

What is claimed is:

1. Method for substantially removing noxious vapors liberated from materials treated with highly halogenated flame retarding agents upon exopsure to heat comprising applying to said materials an organophosphorus comdlcated' pound having the structural formula:

EXAMPLE 1 R The following solutions were respectively prepared and (R')m IL (0R) charged to aerosol bottles. wherein R is a member selected from the group consist- Solvent Getter, Flame retardant, tetrahydro- 0P (OCHJCECH)Q, omoomonrnomnm, iuran, wt. in grams wt. in grams grams Solution 1 e 5.0 45.0 Solution 0. 5 5 t) 44.5 Solution 3 5.0 5 0 40.0 Solution 4 l5. 0 45. 0

The propellant in all four solutions was a mixture of ing of alkynyl, alkenyl and aralkenyl radicals, R is a 32.5 g. Freon II and 17.5 g. Freon 12. member selected from the group consisting of alkyl, halo- Strips of cotton broadcloth, 2" x 10', were sprayed alkyl and alkenyl radicals, m is a whole number from 0 with the above soluitons to a 17% dry weight pick-up. to 1 inclusive, and n is a whole number from 2 to 3 inclu- The resulting cloth strips were held in the open flame sive, such that m+n equals 3, in sufflcient quantities to of a burner for a sufficient period of time to cause burnimpart thereto from about 10 to about 90% by weight of ing or charting and were then removed. The results obsaid compound based on the weight of flame retarding tained are summarized in Table 1 below: agent {herein- TABLE I 2. Method as defined in claim 1 wherein the organophosphorus compound is applied in combination with an Solution 1C1oth charred; vapors very noxious; hand inert vehicle.

stiff; no afterglow. 3. Method as defined in claim 2 wherein the organophosphorus compound is present in the inert vehicle in concentrations ranging from about to about by Weight.

4. Method as defined in claim 1 wherein the organophosphorus compound is an organophosphate represented by the structural formula:

wherein R is a member selected from the group consisting of alkynyl, alkenyl and aralkenyl radicals.

5. Method as defined in claim 4 wherein the orgauophosphate is tripropargyl phosphate.

6. Method as defined in claim 1 wherein the organephosphorus compound is an orgauophosphonate represented by the structural formula:

wherein R is a member selected from the group consisting of alkyl, haloalkyl and alkenyl and R is a member selected from the group consisting of alkynyl, alkenyl and aralkenyl.

7. Method as defined in claim 6 wherein the organophosphonate is dipropargyl 2-ehloroethy1 phosphonate.

References Cited UNITED STATES PATENTS OTHER REFERENCES Cherbuliez et al.: Helvetica Chimica Aeta, vol. 47, pp. 2098-2105 (1964).

Miles et al.: Textile Research Journal, A Laboratory Study pp. 357-362, vol. 39, No. 4, April 1969.

Frick et aL: Textile Research Journal, vol. 25, pp. -105, January 1955.

MURRAY KATZ, Primary Examiner H. J. GWINNELL, Assistant Examiner US. Cl. X.R. 

